Synthesis of cis-1,4-polyisoprene with low-temperature prepared Ti-Al catalysts

doi:10.11949/j.issn.0438-1157.20150032

Abstract

Abstract:

The high cis-1,4-polyisoprene is prepared by Ziegler-Natta coordination polymerization. The effect of preparation method and condition of heterogeneous TiCl₄-Al(i-Bu)₃ two component catalyst on isoprene polymerization are investigated. The influence of several parameters on the catalytic activity, the gel content, intrinsic viscosity, microstructure and cis-1,4-content of the polyisoprene is examined in detail, including mole ratio of catalyst component, prefabricate temperature and aging time as well as catalyst dosage, polymerization temperature and time. The results show that the optimum conditions of catalyst preparation are as follows: the molar ratio of Al/Ti is 1.0, the temperature of prefabricate is at -40℃, the aging time is 2 h at room temperature, molar ratio of Ti/Ip(catalyst content)is 6×10^-3, the polymerization for 5 h at 50℃. Under these condition, the monomer conversion is 87.1% in the polymerization, the microstructure cis-1,4 content in obtained polymer is up to 91.76%.

Key words: catalyst, Ziegler-Natta polymerization, cis-1,4-polyisoprene, low-temperature, multiphase reaction, reactivity

摘要：

采用Ziegler-Natta配位聚合制备了高顺式聚异戊二烯,主要考察了非均相催化体系四氯化钛-三异丁基铝二组分催化剂的预制方法以及催化剂预制条件对异戊二烯体系聚合规律的影响。讨论了催化剂配比、预制催化剂温度和陈化温度对催化剂活性及聚合物的凝胶含量、特征黏度、微观结构含量等方面的影响。同时讨论了催化剂用量、聚合温度和聚合时间对聚合活性及聚合物的凝胶含量、特征黏度、微观含量等方面的影响。研究结果表明,合成高cis-1,4-聚异戊二烯的最佳实验条件为:Al/Ti摩尔比1.0,催化剂预制温度-40℃,陈化2 h,Ti/Ip摩尔比6×10^-3,聚合温度50℃,聚合时间5 h。所得聚合物最高转化率为87.1%,cis-1,4结构含量为91.76%。

关键词: 催化剂, 配位聚合, cis-1,4-聚异戊二烯, 低温, 多相反应, 活性

CLC Number:

TQ333.3

WANG Zhaowei, YU Junwei, LI Xing, LIU Xiaoxuan. Synthesis of cis-1,4-polyisoprene with low-temperature prepared Ti-Al catalysts[J]. CIESC Journal, 2015, 66(7): 2521-2527.

汪昭玮, 于俊伟, 李兴, 刘晓暄. 低温预制钛系催化剂合成cis-1,4-聚异戊二烯[J]. 化工学报, 2015, 66(7): 2521-2527.

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